EP1764376A1 - Verfahren zur Herstellung einer metallorganischen Verbindung mit mindestens einem Zuschauerliganden - Google Patents

Verfahren zur Herstellung einer metallorganischen Verbindung mit mindestens einem Zuschauerliganden Download PDF

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Publication number
EP1764376A1
EP1764376A1 EP05077117A EP05077117A EP1764376A1 EP 1764376 A1 EP1764376 A1 EP 1764376A1 EP 05077117 A EP05077117 A EP 05077117A EP 05077117 A EP05077117 A EP 05077117A EP 1764376 A1 EP1764376 A1 EP 1764376A1
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EP
European Patent Office
Prior art keywords
metal
ligand
sub
formula
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP05077117A
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English (en)
French (fr)
Inventor
Henricus Johannes Arts
Gerardus Henricus Josephus Van Doremaele
Edwin Gerard Ijpeij
Francis Van Der Burgt
Martin Alexander Zuideveld
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DSM IP Assets BV
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DSM IP Assets BV
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Publication date
Application filed by DSM IP Assets BV filed Critical DSM IP Assets BV
Priority to EP05077117A priority Critical patent/EP1764376A1/de
Priority to AT06792035T priority patent/ATE520720T1/de
Priority to EP06792035A priority patent/EP1924611B1/de
Priority to BRPI0616075-1A priority patent/BRPI0616075A2/pt
Priority to KR1020087009004A priority patent/KR101293419B1/ko
Priority to JP2008530411A priority patent/JP5148495B2/ja
Priority to CN2006800340882A priority patent/CN101268106B/zh
Priority to PCT/EP2006/008916 priority patent/WO2007031295A1/en
Priority to US12/066,468 priority patent/US7705172B2/en
Publication of EP1764376A1 publication Critical patent/EP1764376A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the invention relates to a process for the preparation of a metal-organic compound according formula 1: MAL j Y r X (p-(n+v+r) R n (formula 1) where:
  • WO-A1-2005/013663 describes a process for the preparation of a metal-organic compound comprising an imine ligand.
  • Imine ligands for these precatalysts can be guanidine, iminoimidazoline, amidine or a ketimine.
  • CpTiCl 3 is reacted with the imine ligand and the reaction product, being an intermediate dichloride complex, is subsequently alkylated with an organolithium compound or an organomagnesium compound.
  • toluene is an undesired compound in the subsequent polymerisation process (waarom?) and has therefore to be removed from the metal-organic compound.
  • An additional disadvantage of toluene is the fact that it is difficult to remove from the prepared metal-organic compound, and from a polyolefin prepared with a toluene comprising metal-organic compound.
  • a purpose of the present invention is therefore to provide an alternative process for the preparation of a metal-organic compound that can be carried out in an aliphatic hydrocarbon without the above-mentioned disadvantages.
  • a metal-organic compound suitable as precatalyst in olefin polymerisation, can be prepared in an aliphatic hydrocarbon (linear, branched or cyclic) comprising between 3 and 20 carbon atoms, which is generally the same solvent as is used in a subsequent olefin polymerisation.
  • An additional advantage of the method of the invention is, that during the second step of the process, wherein the precursor is contacted with the spectator ligand no solid side products are formed so that purification after this step is not necessary before the precatalyst prepared according to the method of the invention can be applied in a subsequent olefin polymerisation process.
  • the metal-organic compound prepared by the method of the invention has the same performance as a metal-organic compound prepared via known production processes. Another advantage of this method is that multiple extractions and solvent changes, through evaporation of the reaction or extraction solvent and a redisolve in a solvent suitable for the polymerization, can be avoided. A further advantage of the process of the invention is that the process can be carried out at room temperature.
  • a metal organic reagent according to formula 3 MAL j X p-v (formula 3), is contacted with an alkylating agent, thus forming a precursor in which at least one of the halide atoms is replaced by an anionic ligand R.
  • M is a metal of group 3 - 13 or the lanthanide series, and p is the valency of the metal M.
  • the ligand L may be present in the organometallic compound for reasons of stability. If the ligand L is present, L can be an ether, a thioether, a tertiary amine, a tertiary phosphane, an imine, or a bi-, or oligodentate, comprising an ether, a thioether, a tertiary amine, or a tertiary phosphane functional group, or combinations thereof.
  • Suitable ligands A are (substituted) cyclopentadienyl groups, (substituted) indenyl groups, (substituted) fluorenyl groups, (substituted) tetrahydroindenyl groups, (substituted) tetrahydrofluorenyl groups, (substituted) octahydrofluorenyl groups, (substituted) benzoindenyl groups, (substituted) heterocyclopentadienyl groups, (substituted) heteroindenyl groups, (substituted) heterofluorenyl groups, or their isomers.
  • a heterocyclopentadienyl group (hereinafter referred to as 'hetero ligand') is understood to be a group that has been derived from a cyclopentadienyl group, but in which at least one of the C atoms in the 5-ring of the cyclopentadienyl has been replaced by a hetero atom, which heteroatom may be chosen from group 13, 15 or 16. If there is more than one heteroatom present in the 5-ring of the hetero ligand, these heteroatoms may be the same or different. More preferably, the heteroatom is chosen from group 15, while yet more preferably the heteroatom is phosphorus.
  • R is an anionic ligand independently selected from the group consisting of alkyl or arylalkyl, e.g. benzyl, aryl, or a combination thereof.
  • the anionic ligand R is free from ⁇ -hydrogen atoms on an aliphatic carbon atom.
  • anionic ligands free from ⁇ -hydrogen atoms are methyl, and compounds with the general formula -CH 2 -(BR 1 R 2 R 3 ), wherein B can be C, Si or Ge, and the substituents R 1 , R 2 and R 3 can be chosen from the group of (cyclo)aliphatic hydrocarbons, or (substituted) aromatic hydrocarbons.
  • R 1 , R 2 and R 3 can be the same or different, both substituted and unsubstituted.
  • R is preferably methyl or benzyl.
  • the spectator ligand Y represented by formula 2 is covalently bonded to the metal via the imine nitrogen atom.
  • Sub 1 is a substituent that comprises a group 14 atom, preferably a carbon atom through which Sub 1 is bound to the imine carbon atom.
  • Sub 1 preferably represents a hydrocarbyl radical, optionally substituted with heteroatoms of group 13 - 17, or a silyl radical, optionally substituted with group 13-17 atoms.
  • Sub 2 is a substituent, which comprises an atom of group 15-16, through which Sub 2 is bonded to the imine carbon atom.
  • this atom is selected from the group of nitrogen, phosphorus, oxygen or sulfur.
  • Sub 2 preferably is an amide, imide, phosphide, phospinimide, oxide, sulphide radical, optionally substituted with hydrocarbyl radicals or silyl radicals as described for Sub 1 .
  • a metal-organic compound according to the invention exhibits a high efficiency for the polymerization of both ethylene and propylene or copolymers of ethylene and alpha olefins and terpolymers of ethylene, alpha olefins and other polymarizable olefins having one or more double bonds.
  • Catalysts comprising the metal-organic compound according to the invention are particularly suitable for the production of EPDM.
  • the process of the invention is carried out in an aliphatic hydrocarbon with between 3 and 20 carbon atoms.
  • suitable hydrocarbons are isobutane, pentane, isopentane, hexane, cyclohexane, heptane, cycloheptane.
  • Me 5 CpTiCl 3 (580 mg, 2.00 mmol) and N,N-diisopropyl-2,6-difluorobenzamidine (482 mg, 2.01 mmol) were dissolved in hexane (30 ml). Only a small amount of the Me 5 CpTiCl 3 dissolved. Next triethylamine (0.5 ml) was added and the reaction mixture was stirred for 18 hours. The reaction mixture was filtered and the residue was rinsed once with hexanes (30 ml). The hexane of the combined organic phases (filtrate and rinse liquid) was removed in vacuo resulting in 0.44g of products as an orange powder.
  • Me 5 CpTiCl 3 (580 mg, 2.00 mmol) and N,N-diisopropyl-2,6-difluorobenzamidine (488 mg, 2.03 mmol) were dissolved in hexanes (30 ml). Only a small amount of the Me 5 CpTiCl 3 dissolved. Next triethylamine (0.5 ml) was added and the reaction mixture was stirred for 60 hours. The reaction mixture was filtered and the residue was rinsed once with hexanes (50 ml). The solvent of the combined organic phases (filtrate and rinse liquid) was removed in vacuo resulting in 0.33g (33%) of products as an orange powder.
  • Pentamethylcyclopentadienyltitaniumtrichloride (3.09g, 10.7 mmol) were suspended in hexane (50 ml). The suspension was cooled to 0°C and methyllithium solution (1.6M in diethylether, 20.0 ml, 32 mmol) was added dropwise. The mixture was stirred at 0°C for 21 ⁇ 2 hour after which it was allowed to warm to room temperature. Stirring was continued at room temperature for 30 minutes. The solids were filtered off and washed once with hexanes (30 ml). The combined hexane solutions of filtrate and rinse liquid were evaporated to dryness resulting in 2.37g (98%) of light brown product. The product was characterized by 1 H NMR 300 MHz (CDCl 3 ) ⁇ (ppm): 1.9 (s, 15H), 0.7 (s, 9H).
  • Dicyclohexylamine (18.1 g, 0.10 mmol) was dissolved in diethylether (150 ml). The solution was heated to reflux temperature and a solution of methylmagnesiumbromide (33 ml, 3.0M in diethylether, 0.10 mol) was added dropwise over a period of 20 minutes. After the addition, the reaction mixture was stirred for 3 hours at room temperature. Benzonitrile (10.3g, 0.10 mol) was added and the reaction mixture was stirred for 20 hours at room temperature. A solution of ammoniumchloride (10% in water, 100 ml) was added. The water and organic layers were separated and the water layer was extracted twice with diethylether (150 ml).
  • Me 5 CpTiMe 3 (227 mg, 1.00 mmol) and N,N-dicyclohexylbenzamidine (281 mg, 0.99 mmol) are dissolved in hexanes (30 ml). After 2, 4 and 24 hours aliquots of 3ml were taken from the reaction mixture and diluted to 100ml with hexanes. The diluted solutions were used in polymerisation experiments.
  • the reactor was filled with pentamethylheptane (PMH) (950 mL), MAO (Crompton, 10 wt% in toluene), butylated hydroxy toluene (BHT), 5-ethylidene-2-norbornene (ENB) (0.7 mL) and 5-vinyl-2-norbornene (VNB) (0.7 mL).
  • PMH pentamethylheptane
  • MAO Chropton, 10 wt% in toluene
  • BHT butylated hydroxy toluene
  • ENB 5-ethylidene-2-norbornene
  • VNB 5-vinyl-2-norbornene
  • the polymers that were prepared as described in the examples were analyzed by means of Size Exclusion Chromatography (SEC) coupled to Refractive Index (RI) and Differential Viscometry (DV) detection.
  • SEC Size Exclusion Chromatography
  • RI Refractive Index
  • DV Differential Viscometry
  • FT-IR Fourier transformation infrared spectroscopy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
EP05077117A 2005-09-16 2005-09-16 Verfahren zur Herstellung einer metallorganischen Verbindung mit mindestens einem Zuschauerliganden Withdrawn EP1764376A1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP05077117A EP1764376A1 (de) 2005-09-16 2005-09-16 Verfahren zur Herstellung einer metallorganischen Verbindung mit mindestens einem Zuschauerliganden
AT06792035T ATE520720T1 (de) 2005-09-16 2006-09-13 Verfahren zur herstellung einer metallorganischen verbindung mit einem spectator-liganden
EP06792035A EP1924611B1 (de) 2005-09-16 2006-09-13 Verfahren zur herstellung einer metallorganischen verbindung mit einem spectator-liganden
BRPI0616075-1A BRPI0616075A2 (pt) 2005-09-16 2006-09-13 processo para a preparação de um composto organometálico compreendendo um ligante espectador
KR1020087009004A KR101293419B1 (ko) 2005-09-16 2006-09-13 구경꾼 리간드를 포함하는 금속-유기 화합물의 제조방법
JP2008530411A JP5148495B2 (ja) 2005-09-16 2006-09-13 スペクテーター配位子を含む有機金属化合物の調製方法
CN2006800340882A CN101268106B (zh) 2005-09-16 2006-09-13 用于制备包括旁观配体的金属有机化合物的方法
PCT/EP2006/008916 WO2007031295A1 (en) 2005-09-16 2006-09-13 Process for the preparation of a metal-organic compound comprising a spectator ligand
US12/066,468 US7705172B2 (en) 2005-09-16 2006-09-13 Process for the preparation of a metal-organic compound comprising a spectator ligand

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05077117A EP1764376A1 (de) 2005-09-16 2005-09-16 Verfahren zur Herstellung einer metallorganischen Verbindung mit mindestens einem Zuschauerliganden

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EP05077117A Withdrawn EP1764376A1 (de) 2005-09-16 2005-09-16 Verfahren zur Herstellung einer metallorganischen Verbindung mit mindestens einem Zuschauerliganden
EP06792035A Not-in-force EP1924611B1 (de) 2005-09-16 2006-09-13 Verfahren zur herstellung einer metallorganischen verbindung mit einem spectator-liganden

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US (1) US7705172B2 (de)
EP (2) EP1764376A1 (de)
JP (1) JP5148495B2 (de)
KR (1) KR101293419B1 (de)
CN (1) CN101268106B (de)
AT (1) ATE520720T1 (de)
BR (1) BRPI0616075A2 (de)
WO (1) WO2007031295A1 (de)

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Publication number Priority date Publication date Assignee Title
WO2009063084A2 (en) * 2007-11-15 2009-05-22 Dsm Ip Assets Bv Process for the preparation of ultra high molecular weight polyethylene
JP6691009B2 (ja) * 2016-07-05 2020-04-28 株式会社Adeka 金属炭化物含有薄膜形成用原料及び金属炭化物含有薄膜の製造方法
EP3409697A1 (de) 2017-05-28 2018-12-05 SABIC Global Technologies B.V. Zubereitung von polymerdispersionen
KR20240073969A (ko) * 2021-10-08 2024-05-27 엔테그리스, 아이엔씨. 유기-티타늄 화합물의 제조 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114481A (en) * 1997-09-15 2000-09-05 Nova Chemicals (International) S.A. Catalyst having a ketimide ligand
WO2002070569A1 (en) * 2001-03-05 2002-09-12 Stichting Dutch Polymer Institute Olefin polymerization catalyst component and catalyst system and polymerization process using such a catalyst system
WO2005014666A1 (en) * 2003-08-04 2005-02-17 Dsm Ip Assets B.V. Process for the preparation of a metal-organic compound comprising at least one imine ligand

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11236410A (ja) * 1998-02-20 1999-08-31 Nippon Polyolefin Kk 超高分子量エチレン系重合体の製造方法
DE19924176A1 (de) * 1999-05-27 2000-11-30 Bayer Ag Katalysatorsystem auf Basis von Fulvenverbindungen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114481A (en) * 1997-09-15 2000-09-05 Nova Chemicals (International) S.A. Catalyst having a ketimide ligand
WO2002070569A1 (en) * 2001-03-05 2002-09-12 Stichting Dutch Polymer Institute Olefin polymerization catalyst component and catalyst system and polymerization process using such a catalyst system
WO2005014666A1 (en) * 2003-08-04 2005-02-17 Dsm Ip Assets B.V. Process for the preparation of a metal-organic compound comprising at least one imine ligand
WO2005014665A1 (en) * 2003-08-04 2005-02-17 Dsm Ip Assets B.V. Process for the preparation of a metalloorganic compound comprising at least one imine ligand
WO2005014663A1 (en) 2003-08-04 2005-02-17 Dsm Ip Assets B.V. Process for the preparation of an metalloorganic compound comprising at least one imine ligand

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ORGANOMETALLICS, vol. 8, 1989, pages 376 - 382

Also Published As

Publication number Publication date
WO2007031295A1 (en) 2007-03-22
JP5148495B2 (ja) 2013-02-20
CN101268106B (zh) 2010-08-25
US7705172B2 (en) 2010-04-27
BRPI0616075A2 (pt) 2011-06-07
EP1924611A1 (de) 2008-05-28
US20090137830A1 (en) 2009-05-28
EP1924611B1 (de) 2011-08-17
ATE520720T1 (de) 2011-09-15
JP2009507873A (ja) 2009-02-26
CN101268106A (zh) 2008-09-17
KR101293419B1 (ko) 2013-08-05
KR20080059210A (ko) 2008-06-26

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